Sharp raman anomalies and broken adiabaticity at a pressure induced transition from band to topological insulator in Sb2Se3

The nontrivial electronic topology of a topological insulator is thus far known to display signatures in a robust metallic state at the surface. Here, we establish vibrational anomalies in Raman spectra of the bulk that signify changes in electronic topology: an E-g(2) phonon softens unusually and its linewidth exhibits an asymmetric peak at the pressure induced electronic topological transition (ETT) in Sb2Se3 crystal. Our first-principles calculations confirm the electronic transition from band to topological insulating state with reversal of parity of electronic bands passing through a metallic state at the ETT, but do not capture the phonon anomalies which involve breakdown of adiabatic approximation due to strongly coupled dynamics of phonons and electrons. Treating this within a four-band model of topological insulators, we elucidate how nonadiabatic renormalization of phonons constitutes readily measurable bulk signatures of an ETT, which will facilitate efforts to develop topological insulators by modifying a band insulator. DOI: 10.1103/PhysRevLett.110.107401

Contrast in luminescence characteristics (intense UV to bright visible light) of ZnO nanostructures with the variation in microstructure

We report the controlled variation of luminescence of ZnO nanostructures from intense ultraviolet to bright visible light. Deliberate addition of surfactants in the reaction medium not only leads to growth anisotropy of ZnO, but also alters the luminescence property. ZnO nanoclusters comprising of very fine particles with crystallite sizes approximate to 15-22nm were prepared in a non-aqueous medium, either from a single alcohol or from their mixtures. Introduction of the aqueous solution of the surfactant helps in altering the microstructure of ZnO nanostructure to nanorods, nanodumb-bells as well as the luminescence property. The as-prepared powder material is found to be well crystallized. Defects introduced by the surfactant in aqueous medium play an important role in substantial transition in the optical luminescence. Chromaticity coordinates were found to lie in the yellow region of color space. This gives an impression of white light emission from ZnO nanocrystals, when excited by a blue laser. Oxygen vacancy is described as the major defect responsible for visible light emission as quantified by X-ray photoelectron spectroscopy and Raman analysis.

Density Functional Theoretical Modeling, Electrostatic Surface Potential and Surface Enhanced Raman Spectroscopic Studies on Biosynthesized Silver Nanoparticles: Observation of 400 pM Sensitivity to Explosives

Interaction of adsorbate on charged surfaces, orientation of the analyte on the surface, and surface enhancement aspects have been studied. These aspects have been explored in details to explain the surface-enhanced Raman spectroscopic (SERS) spectra of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (HNIW or CL-20), a well-known explosive, and 2,4,6-trinitrotoluene (TNT) using one-pot synthesis of silver nanoparticles via biosynthetic route using natural precursor extracts of clove and pepper. The biosynthesized silver nanoparticles (bio Ag Nps) have been characterized using UV-vis spectroscopy, scanning electron microscopy and atomic force microscopy. SERS studies conducted using bio Ag Nps on different water insoluble analytes, such as CL-20 and TNT, lead to SERS signals at concentration levels of 400 pM. The experimental findings have been corroborated with density functional computational results, electrostatic surface potential calculations, Fukui functions and potential measurements.

Solvatochromism of 9,10-phenanthrenequinone: An electronic and resonance Raman spectroscopic study

Solvent effects play a vital role in various chemical, physical, and biological processes. To gain a fundamental understanding of the solute-solvent interactions and their implications on the energy level re-ordering and structure, UV-VIS absorption, resonance Raman spectroscopic, and density functional theory calculation studies on 9,10-phenanthrenequinone (PQ) in different solvents of diverse solvent polarity has been carried out. The solvatochromic analysis of the absorption spectra of PQ in protic dipolar solvents suggests that the longest (1n-pi(1)*; S-1 state) and the shorter (1 pi-pi(1)*; S-2 state) wavelength band undergoes a hypsochromic and bathochromic shift due to intermolecular hydrogen bond weakening and strengthening, respectively. It also indicates that hydrogen bonding plays a major role in the differential solvation of the S-2 state relative to the ground state. Raman excitation profiles of PQ (400-1800 cm(-1)) in various solvents followed their corresponding absorption spectra therefore the enhancements on resonant excitation are from single-state rather than mixed states. The hyperchromism of the longer wavelength band is attributed to intensity borrowing from the nearby allowed electronic transition through vibronic coupling. Computational calculation with C-2 nu symmetry constraint on the S-2 state resulted in an imaginary frequency along the low-frequency out-of-plane torsional modes involving the C=O site and therefore, we hypothesize that this mode could be involved in the vibronic coupling. (C) 2015 AIP Publishing LLC.

Pressure-induced structural phase transitions and phonon anomalies in ReO3: Raman and first-principles study

We report high-pressure Raman-scattering studies on single-crystal ReO3 up to 26.9 GPa at room temperature, complemented by first-principles density functional calculations to assign the modes and to develop understanding of the subtle features of the low-pressure phase transition. The pressure (P) dependence of phonon frequencies (omega) reveals three phase transitions at 0.6, 3, and 12.5 GPa with characteristic splitting and changes in the slope of omega(P). Our first-principles theoretical analysis confirms the role of the rotational modes of ReO6, M-3, to the lowest pressure structural transition, and shows that the transition from the Pm3m to the Im3 structure is a weak first-order transition, originating from the strong anharmonic coupling of the M-3 modes with the acoustic modes (strain).

Enhanced UV detection by non-polar epitaxial GaN films

Nonpolar a-GaN (11-20) epilayers were grown on r-plane (1-102) sapphire substrates using plasma assisted molecular beam epitaxy. High resolution x-ray diffractometer confirmed the orientation of the grown film. Effect of the Ga/N ratio on the morphology and strain of a-GaN epilayers was compared and the best condition was obtained for the nitrogen flow of 1 sccm. Atomic force microscopy was used to analyze the surface morphology while the strain in the film was quantitatively measured using Raman spectroscopy and qualitatively analyzed by reciprocal space mapping technique. UV photo response of a-GaN film was measured after fabricating a metal-semiconductor-metal structure over the film with gold metal. The external quantum efficiency of the photodetectors fabricated in the (0002) polar and (11-20) nonpolar growth directions were compared in terms of responsivity and nonpolar GaN showed the best sensitivity at the cost of comparatively slow response time. (C) 2015 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

Hydrogen content estimation of hydrogenated amorphous carbon by visible Raman spectroscopy

In the present study, we report the hydrogen content estimation of the hydrogenated amorphous carbon (a-C:H) films using visible Raman spectroscopy in a fast and nondestructive way. Hydrogenated diamondlike carbon films were deposited by the plasma enhanced chemical vapor deposition, plasma beam source, and integrated distributed electron cyclotron resonance techniques. Methane and acetylene were used as source gases resulting in different hydrogen content and sp2/sp3 fraction. Ultraviolet-visible (UV-Vis) spectroscopic ellipsometry (1.5-5 eV) as well as UV-Vis spectroscopy were provided with the optical band gap (Tauc gap). The sp2/sp3 fraction and the hydrogen content were independently estimated by electron energy loss spectroscopy and elastic recoil detection analysis-Rutherford back scattering, respectively. The Raman spectra that were acquired in the visible region using the 488 nm line shows the superposition of Raman features on a photoluminescence (PL) background. The direct relationship of the sp2 content and the optical band gap has been confirmed. The difference in the PL background for samples of the same optical band gap (sp2 content) and different hydrogen content was demonstrated and an empirical relationship between the visible Raman spectra PL background slope and the corresponding hydrogen content was extracted. © 2004 American Institute of Physics.

Band gap opening of graphene after UV/ozone and oxygen plasma treatments

Graphene grown by Chemical Vapor Deposition (CVD) on nickel subsrate is oxidized by means of oxygen plasma and UV/Ozone treatments to introduce bandgap opening in graphene. The degree of band gap opening is proportional to the degree of oxidation on the graphene. This result is analyzed and confirmed by Scanning Tunnelling Microscopy/Spectroscopy and Raman spectroscopy measurements. Compared to conventional wet-oxidation methods, oxygen plasma and UV/Ozone treatments do not require harsh chemicals to perform, allow faster oxidation rates, and enable site-specific oxidation. These features make oxygen plasma and UV/Ozone treatments ideal candidates to be implemented in high-throughput fabrication of graphene-based microelectronics. © 2011 Materials Research Society.

Raman scattering and photoluminescence studies of Zn1-xMnxO nanowires via vapor phase growth

In this paper, we investigated the Raman scattering and photoluminescence of Zn1-xMnxO nanowires synthesized by the vapor phase growth. The changes of E-2(High) and A(1(LO)) phonon frequency in Raman spectra indicate that the tensile stress increases while the free carrier concentration decreases with the increase of manganese. The Raman spectra exited by the different lasers exhibit the quantum confinement effect of Zn1-xMnxO nanowires. The photoluminescence spectra reveal that the near band emission is affected by the content of manganese obviously. The values Of I-UV/G decrease distinctly with the manganese increase also demonstrate that more stress introduced with the more substitution of Mn for Zn.

Homoepitaxial growth of 4H-SiC multi-epilayers and its application to UV detection

Homoepitaxial growth of 4H-SiC p(+)/pi/n(-) multi-epilayer on n(+) substrate and in-situ doping of p(+) and pi-epilayer have been achieved in the LPCVD system with SiH4+C2H4+H-2. The surface morphologies, homogeneities and doping concentrations of the n(-)-single-epilayers and the p(+)/pi/n(-) multi-epilayers were investigated by Nomarski, AFM, Raman and SIMS, respectively. AFM and Raman investigation showed that both single- and,multi-epilayers have good surface morphologies and homogeneities, and the SIMS analyses indicated the boron concentration in p+ layer was at least 100 times higher than that in pi layer. The UV photodetectors fabricated on 4H-SiC p(+)/pi/n(-) multi-epilayers showed low dark current and high detectivity in the UV range.

硼磷酸盐及相关基质中稀土离子的UV－VUV光谱和XAFS

采用高温固相反应合成了稀土离子激活的碱土硼磷酸盐MBPO_5:RE（M=Ca, Sr, Ba；RE＝Sm, Eu, Tb, Dy), Ba_3BPO_7:RE和Ba_3BP_O_(12):RE、稀土硼磷酸盐Ln_7BP_2P_(17):RE (Ln=La, Gd)、碱土（稀土）磷酸盐M_3(PO_4)_2:RE (M=Sr, Ba),ABLa(PP_4)_2:Ce,Tb (A=K, Na;B＝Mg, Zn）、碱土（稀土）硼酸盐SrB_4O_7:RE（Re＝Sm, Eu），BaB_8O_(13):Eu，SrB_6O_(10):Sm, M_3Gd_2(BO_3）_4:RE (M＝Ca, Sr)，B_3O6:Eu(RE=La, Gd)和稀土硼钨酸盐Cd_3BWO_9:Eu。通过XRD、IR光谱和Raman光谱等表征了其结构。测定了上述19个基质的数十个发光体的UV佩VUV光谱和RE-L_3（RE=Sm,Eu, Gd)边的XANES和EXAFS。碱土硼磷酸盐Ba_3BPO_7和Ba_3BP_3O_(12)、稀土硼磷酸盐Ln_7BP_2O_(17) (Ln=La, Gd)和稀土钨硼酸盐Gd3Bwo9等6个基质中稀土离子的UV-VUV光谱和除个别基质（REB_3O_6等）外的VUV光谱均属首次报道。发现土稀土离子激活的这些发光体在VUV范围有丰富的基质吸收带。认为基质中阴离子的结构和基质的晶体结构可能是影响基质的吸收带位置的重要因素。通过XANEs和UV-VUV光谱的联系，结合经验公式首次确证了一些复合氧化物基质中一些RE~(3＋)在vuv范围的f-d跃迁位置。根据VUV光谱测定结果推测了一些基质中RE~(3+)的CTB位置。首次应用RE-L_3边的XANES和UV-VUV光谱两种方法分析比较了RE~(3＋)(RE=Eu, Sm)离子在空气条件下在碱土硼磷酸盐、硼酸盐和磷酸盐基质中的还原。首次应用高分辨发射光谱和RE-L_3边的EXAFS研究了在一些基质中发光中心的配位数、键长和格位对称性等结构因素。

Fabrication, characterization, and application in surface-enhanced Raman spectrum of assembled type-I collagen-silver nanoparticle multilayered films

In this paper, we report a facile method for the fabrication of type-I collagen-silver nanoparticles (Ag NPs) multilayered films by utilizing type-I collagen as a medium. These samples were characterized by UV-vis spectra photometer, atomic force microscopy, scanning electron microscopy, and Fourier transform IR spectrum. Experimental results show that collagen molecules serve as effective templates to assemble Ag NPs into multilayer films. These samples exhibit high surface-enhanced Raman scattering (SERS) enhancement abilities.

Monitoring catalytic degradation of dye molecules on silver-coated ZnO nanowire arrays by surface-enhanced Raman spectroscopy

Catalytic degradation of organic dye molecules has attracted extensive attention due to their high toxicity to water resources. In this paper, we propose a novel method for the fabrication of uniform silver-coated ZnO nanowire arrays. The degradation of typical dye molecule rhodamine 6G (R6G), as an example, is investigated in the presence of the as-prepared silver-coated ZnO nanowire arrays. The experimental results show that such composite nanostructures exhibit high catalytic activity, and the reaction follows pseudo-first-order kinetics. Furthermore, these nanowire arrays are desirable SERS substrates for monitoring the catalytic degradation of dye molecules. Compared with traditional UV-visible spectroscopy, SERS technology can reflect more truly the catalytic degradation process occurring on the surface of the catalysts.

Characterization and optimization of AuNPs labeled by Raman reporters on glass based on silver enhancement

In this report, gold nanoparticles (AuNPs) labeled by Raman reporters (AuNPs-R6G) were assembled on glass and used as the seeds to in situ grow silver-coated nanostructures based on silver enhancer solution, forming the nanostructures of AuNPs-R6G@Ag, which were characterized by scanning electron microscopy (SEM) and UV-visible spectroscopy. More importantly, the obtained silver-coated nanostructures can be used as a surface enhancement Raman scattering (SERS) substrate. The different SERS activities can be controlled by the silver deposition time and assembly time of AuNPs-R6G on glass. The results indicate that the maximum SERS activity could be obtained on AuNPs-R6G when these nanostructures were assembled on glass for 2 h with silver deposition for 2 min.